WO2016061329A1 - Produits composites du bâtiment et procédés associés - Google Patents

Produits composites du bâtiment et procédés associés Download PDF

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Publication number
WO2016061329A1
WO2016061329A1 PCT/US2015/055706 US2015055706W WO2016061329A1 WO 2016061329 A1 WO2016061329 A1 WO 2016061329A1 US 2015055706 W US2015055706 W US 2015055706W WO 2016061329 A1 WO2016061329 A1 WO 2016061329A1
Authority
WO
WIPO (PCT)
Prior art keywords
composite
calcium sulfate
whiskers
percent
stucco
Prior art date
Application number
PCT/US2015/055706
Other languages
English (en)
Inventor
Mianxue Wu
Jeffery T. FIELDS
Sara E. ENDRES
Original Assignee
Georgia-Pacific Gypsum Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Georgia-Pacific Gypsum Llc filed Critical Georgia-Pacific Gypsum Llc
Publication of WO2016061329A1 publication Critical patent/WO2016061329A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/007—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore distribution, e.g. inhomogeneous distribution of pores
    • C04B38/0074—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore distribution, e.g. inhomogeneous distribution of pores expressed as porosity percentage
    • E—FIXED CONSTRUCTIONS
    • E04—BUILDING
    • E04C—STRUCTURAL ELEMENTS; BUILDING MATERIALS
    • E04C2/00—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels
    • E04C2/02—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials
    • E04C2/04—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres
    • E04C2/043—Building elements of relatively thin form for the construction of parts of buildings, e.g. sheet materials, slabs, or panels characterised by specified materials of concrete or other stone-like material; of asbestos cement; of cement and other mineral fibres of plaster
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials

Definitions

  • the present disclosure relates generally to the field of calcium sulfate-based products, and more particularly to calcium sulfate whiskers and composites and methods for their use and manufacturing.
  • Gypsum (calcium sulfate) panels are commonly used as sheathing panels in wall, door, floor, ceiling, roof, and other building applications. Lightweight gypsum panels are desirable for construction applications, for easier handling and installation. However, these lightweight boards should be manufactured to experience minimal loss of strength and integrity as compared to traditional boards.
  • the second method involves incorporating hollow microspheres into the gypsum stucco slurry to decrease the density of the resulting board.
  • this method can result in uneven density throughout the board and layer separation, for example due to the packing density of the microspheres being much lower than the slurry, resulting in diminished strength and integrity of the board.
  • methods of manufacturing calcium sulfate composites including combining dihydrate calcium sulfate whiskers, hemihydrate calcium sulfate stucco, and water to form a slurry, and setting the slurry to form a composite having a natural porosity of about 60 volume percent or greater.
  • calcium sulfate composites including dihydrate calcium sulfate whiskers and dihydrate calcium sulfate crystals, and having a natural porosity of about 60 volume percent or greater.
  • FIG. 1 is a photograph showing the pore structure of a calcium sulfate whisker composite at low magnification.
  • FIG. 2 is a micrograph showing the crystal and pore structure of a calcium sulfate whisker composite at high magnification.
  • FIG. 3 is a micrograph showing the calcium sulfate whisker morphology of a calcium sulfate whisker slurry prior to ageing.
  • FIG. 4 is a micrograph showing the calcium sulfate whisker morphology of a calcium sulfate whisker slurry after ageing.
  • FIG. 5 is a photograph showing the pore structure of a prior art foamed composite at low magnification.
  • the term “whiskers” refers to single crystal fibers having an aspect ratio greater than 1.
  • the term “aspect ratio” refers to the ratio of the length of a calcium sulfate whisker to its diameter, and the “mean aspect ratio” is the ratio of the average whisker length to the average whisker diameter for a plurality of whiskers.
  • the whiskers disclosed herein are made using calcium sulfate, which may also be referred to as gypsum.
  • Calcium sulfate may exist as a hemihydrate (CaS0 4 *1 ⁇ 2H 2 0), a dihydrate (CaS0 4 *2H 2 0), or an anhydrite (CaS0 4 ).
  • CaS0 4 calcium sulfate hemihydrate
  • calcium sulfate hemihydrate may be used to prepare calcium sulfate whiskers.
  • suitable whiskers such as magnesium oxysulfate, may also be used.
  • methods of manufacturing composites including: (i) combining dihydrate calcium sulfate whiskers, hemihydrate calcium sulfate stucco, and water to form a slurry; and (ii) setting the slurry to form a composite having a natural porosity of about 60 volume percent or greater.
  • natural porosity refers to the air space within the composite that forms as the composite sets, as opposed to being induced in the composite.
  • known techniques utilizing microspheres and foaming agents result in an induced porosity of the composite.
  • the dihydrate calcium sulfate whiskers and the hemihydrate calcium sulfate stucco are combined in amounts from about 1 percent by weight whiskers to about 35 percent by weight whiskers and from about 65 percent by weight stucco to about 99 percent by weight stucco, as measured on a dry basis.
  • the dihydrate calcium sulfate whiskers and the hemihydrate calcium sulfate stucco may be combined in amounts of about 80 percent by weight stucco and about 20 percent by weight whiskers, as measured on a dry basis.
  • the dihydrate calcium sulfate whiskers and the hemihydrate calcium sulfate stucco may be combined in amounts of about 90 percent by weight stucco and about 10 percent by weight whiskers, as measured on a dry basis.
  • the dihydrate calcium sulfate whiskers are combined with the stucco and water in an amount at or above a predetermined percolation threshold.
  • percolation refers to the long-range, or overall (i.e., instead of localized whisker-to-whisker interconnection), tendency of the whiskers to be individualized and interconnected in the stucco. That is, when percolation is reached, a network of whiskers begins to form, such that shrinkage of the composite slows dramatically. Without being bound by a particular theory, it is believed that porosity can be created in a composite naturally, using tailored whisker geometry to achieve whisker-to-whisker percolation.
  • the packing density of the whiskers can be minimized while the natural porosity of the composite can be maximized, thereby improving the consistency of the porosity throughout the board as well as the amount of porosity of the board.
  • the percolation threshold of the whiskers can be lowered by making whiskers with a higher aspect ratio via a diluted slurry for crystals to freely grow and/or by making whiskers individualized via an "aging" process so that the whiskers take a long time to be separated.
  • the predetermined percolation threshold may be determined using percolation models, such as those disclosed by Yi and Sastry in "Analytical approximation of the percolation threshold for overlapping ellipsoids of revolution," Proc. R. Soc. Lond. A (2004) 460, 2353-2380, which is incorporated herein by reference.
  • percolation models such as those disclosed by Yi and Sastry in "Analytical approximation of the percolation threshold for overlapping ellipsoids of revolution," Proc. R. Soc. Lond. A (2004) 460, 2353-2380, which is incorporated herein by reference.
  • These models indicate that the percolation threshold of whisker-to-whisker percolation can be predicted as function of whisker aspect ratio and of the amount of whiskers present. It has been determined that the greater the aspect ratio of the whiskers, the smaller the critical mass necessary to achieved percolation.
  • the percolation threshold can be determined for whiskers having a known aspect ratio. As used herein percentages given are volume percentages, unless otherwise specified.
  • Whisker clustering is also believed to affect the percolation threshold, and can be used to predict the amount of whiskers having a given aspect ratio that is necessary to achieve percolation.
  • the percolation threshold may range from about 2 volume percent of whiskers for no clustering/agglomeration (i.e., minimum packing and maximum porosity), to about 6 volume percent where whisker clusters of about 3 whiskers per cluster occur, and to much greater than 6 volume percent where whisker clusters of much great than 3 whiskers per cluster occur (i.e., maximum packing, minimum porosity).
  • the percolation threshold amount of whiskers can be determined based on the aspect ratio of the whiskers and the observed agglomeration tendency of the whiskers. Whiskers may be combined with the stucco at or above the threshold amount to build a framework for the overall composite structure and hinder the shrinkage of the gypsum-water structure, without using foaming agents or microspheres.
  • the whiskers have a mean aspect ratio of at least about 2.
  • the whiskers may have a mean aspect ratio from about 2 to about 20.
  • the whiskers have a mean aspect ratio from about 10 to about 20.
  • the whiskers may have an aspect ratio from about 2 to about 30.
  • percolation models may be used to determine the amount of whiskers to add to the stucco to achieve the desired porosity.
  • composites made by these methods may display a natural porosity of about 60 volume percent or greater, such as from about 60 volume percent to about 99 volume percent.
  • the composite has a natural porosity of about 75 volume percent or greater.
  • the composite may have a natural porosity of about 80 volume percent, about 90 percent, or from about 75 to about 95 volume percent.
  • composites made by these methods have a density of about 40 lb/ft 3 or less (approximately 640 kg/m 3 or less).
  • the composites may have a density of about 30 lb/ft 3 or less (approximately 480 kg/m 3 or less).
  • composites made by these methods have a density from about 20 lb/ft 3 to about 50 lb/ft 3 (approximately 320 kg/m 3 to 800 kg/m 3 ).
  • these methods produce lightweight composite boards without the use of foaming agents or microspheres.
  • the combination of dihydrate calcium sulfate whiskers, hemihydrate calcium sulfate stucco, and water results in the conversion of the hemihydrate particles into dihydrate particles, during the mixing and setting steps.
  • the set composite contains dihydrate whiskers and crystal particles.
  • the combining and setting steps may include any suitable methods, such as mixing, allowing the composite to set at room temperature, and/or drying the composite.
  • the methods may further include steps to make the dihydrate calcium sulfate whiskers for use in composite manufacturing.
  • the method further includes: (i) combining hemihydrate calcium sulfate stucco and water to form a slurry of dihydrate calcium sulfate crystals; and (ii) ageing the slurry under ambient conditions to form dihydrate calcium sulfate whiskers in water.
  • the ratio of stucco to water and the ageing period may be tailored to achieve the desired whisker geometry.
  • the method also includes removing at least a portion of the water from the dihydrate calcium sulfate whiskers in water to form dewatered calcium sulfate whiskers.
  • the step of dewatering includes filtering, vacuuming, centrifuging, or a combination thereof.
  • a screen filter may be used to dewater the whiskers.
  • the dihydrate calcium sulfate whiskers are wet dihydrate calcium sulfate whiskers that have been dewatered to about 50 percent water to about 70 percent water, as measured by weight of the wet whiskers.
  • whiskers used in the composite manufacturing steps may be prepared through a simple process at ambient pressure/temperature that does not require autoclaving or high temperature burning like other whisker-forming methods.
  • composites are also provided.
  • the composites may be those manufactured according to any of the methods described above.
  • a composite includes dihydrate calcium sulfate whiskers and dihydrate calcium sulfate crystals, and has a natural porosity of about 60 volume percent or greater. In one embodiment, the composite has a natural porosity from about 60 volume percent to about 99 volume percent. For example, the composite may have a natural porosity of about 75 volume percent or greater. For example, the composite may have a natural porosity of about 80 volume percent or about 90 percent. In one embodiment, the composite has a natural porosity of about 90 volume percent or greater.
  • the composite has a density of about 40 lb/ft 3 or less
  • the composite may have a density of about 30 lb/ft 3 or less (approximately 480 kg/m 3 or less). In one embodiment, the composite has a density from about 20 lb/ft 3 to about 50 lb/ft 3 (approximately 320 kg/m 3 to 800 kg/m 3 ).
  • the composite is a gypsum board having a thickness of about 1 inch (2.54 cm) or less and an area density of about 1500 lb/msf (approximately 7300 g/m 2 ) or less. In one embodiment, the composite is a gypsum board having a thickness of about 1 inch (2.54 cm) or less and an area density of about 1200 lb/msf (approximately 5900 g/m 2 ) or less.
  • the composite may have an area density from about 1000 lb/msf to about 2000 lb/msf (approximately 4900 g/m 2 to 9800 g/m 2 ), with a thickness from about 1/16 inch (0.16) cm to about 1 inch (2.54 cm).
  • Sample 1 contained 65% stucco and 35% dihydrate (DH) whiskers having a mean aspect ratio between 10 and 15, as measured on a dry basis, in the slurry.
  • Sample 2 contained 80% stucco and 20% DH whiskers, as measured on a dry basis, in the slurry.
  • the ingredients were combined and mixed in a glass blender on high for 5-10 seconds. The mixed slurry was then poured into a 4 inch x 4 inch mold and allowed to set into a 1 ⁇ 2 inch thick board.
  • DILOFLO Dispersant
  • Sample 1 had a porosity of approximately 80%, with an area density of approximately 1200 lb/msf for the 1 ⁇ 2 inch board.
  • Sample 2 had a porosity of approximately 75%, with an area density of approximately 1500 lb/msf for the 1 ⁇ 2 inch board.
  • FIG. 1 is a low magnification photograph of the cross-section of the board of Sample 1, showing its pore structure.
  • FIG. 2 is a high magnification micrograph of Sample 1, showing its crystal and pore structure. It was observed that the natural pore size is smaller and more uniform than the induced pores that result in similar board using foaming agents or microspheres. This is evidenced by a comparison of FIG. 1, which shows the small pore size and uniformity of pores in the composite board having a weight of 1220 pounds/msf of Sample 1, and FIG. 5, which shows a prior art composite board made with a foaming agent and having a weight of 1300 pounds/msf.
  • the prior art board of FIG. 5 has significantly larger, and less uniform, pores, than a similar composite made using the calcium sulfate whiskers described herein.
  • FIGS. 3 and 4 are micrographs showing the calcium sulfate whisker morphology of a calcium sulfate whisker slurry at two times during the ageing process (FIG. 4 being after ageing and dispersing of the whiskers occurs, and FIG. 3 being prior to ageing). That is, these micrographs show the ability to tailor the dihydrate whisker morphology (both length and agglomeration) to minimize packing density and maximize natural porosity. ⁇ f - lEy ⁇ ⁇ )
  • a porous composite having smaller pores will display higher strength. Accordingly, the composites disclosed herein will have a higher strength than composites having larger pores, such as those made using foaming agents or microspheres. Moreover, the composites disclosed herein display a more uniform board makeup than those having induced porosity, such that the board integrity is improved.
  • the disclosed high porosity lightweight boards offer easier installation and handling with little to no loss of board strength or integrity, as compared to traditional boards. Moreover, these boards offer improved strength properties as compared to known methods for producing lightweight boards.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Civil Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)

Abstract

L'invention concerne des procédés de fabrication de composites, consistant à combiner des barbes de sulfate de calcium dihydraté, de l'enduit chaux-ciment de sulfate de calcium semi-hydraté, et de l'eau pour former une suspension, et à durcir ladite suspension pour former un composite ayant une porosité naturelle supérieure ou égale à environ 60 pour cent en volume. L'invention concerne également des composites, comprenant des barbes de sulfate de calcium dihydraté et des cristaux de sulfate de calcium dihydraté, et ayant une porosité naturelle supérieure ou égale à environ 60 pour cent en volume.
PCT/US2015/055706 2014-10-16 2015-10-15 Produits composites du bâtiment et procédés associés WO2016061329A1 (fr)

Applications Claiming Priority (2)

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US201462064506P 2014-10-16 2014-10-16
US62/064,506 2014-10-16

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111607827A (zh) * 2019-07-16 2020-09-01 北新集团建材股份有限公司 一种硫酸钙晶须的后处理方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115323476B (zh) * 2022-07-28 2023-09-12 广东邦普循环科技有限公司 磷石膏净化提纯制备硫酸钙晶须的方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4906449A (en) * 1987-10-13 1990-03-06 Toto Ltd. Method for hydrating hemihydrate gypsum
US4965031A (en) * 1989-02-24 1990-10-23 The Celotex Corporation Continuous production of gypsum board
CN1477242A (zh) * 2003-07-08 2004-02-25 宁夏建筑材料研究院 一种石膏晶须及其制造方法和应用
US20060029786A1 (en) * 2004-08-03 2006-02-09 Lance Wang Gypsum boards having glass fiber reinforcement with tacky compliant interface therebetween
US20080152945A1 (en) * 2006-12-20 2008-06-26 David Paul Miller Fiber reinforced gypsum panel

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7116129B2 (en) * 2004-07-20 2006-10-03 Micron Technology, Inc. Temperature-compensated output buffer method and circuit
US7849649B2 (en) * 2005-01-27 2010-12-14 United States Gypsum Company Non-combustible reinforced cementitious lightweight panels and metal frame system for shear walls
US20070122604A1 (en) * 2005-11-28 2007-05-31 Lance Wang Gypsum board and process of manufacture
WO2012122102A2 (fr) * 2011-03-10 2012-09-13 Georgia-Pacific Gypsum Llc Panneau de placoplâtre léger

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4906449A (en) * 1987-10-13 1990-03-06 Toto Ltd. Method for hydrating hemihydrate gypsum
US4965031A (en) * 1989-02-24 1990-10-23 The Celotex Corporation Continuous production of gypsum board
CN1477242A (zh) * 2003-07-08 2004-02-25 宁夏建筑材料研究院 一种石膏晶须及其制造方法和应用
US20060029786A1 (en) * 2004-08-03 2006-02-09 Lance Wang Gypsum boards having glass fiber reinforcement with tacky compliant interface therebetween
US20080152945A1 (en) * 2006-12-20 2008-06-26 David Paul Miller Fiber reinforced gypsum panel

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111607827A (zh) * 2019-07-16 2020-09-01 北新集团建材股份有限公司 一种硫酸钙晶须的后处理方法
CN111607827B (zh) * 2019-07-16 2022-01-07 北新集团建材股份有限公司 一种硫酸钙晶须的后处理方法

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US20160107937A1 (en) 2016-04-21
US10246378B2 (en) 2019-04-02

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